EP1294673B1 - Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst - Google Patents

Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst Download PDF

Info

Publication number
EP1294673B1
EP1294673B1 EP01945647A EP01945647A EP1294673B1 EP 1294673 B1 EP1294673 B1 EP 1294673B1 EP 01945647 A EP01945647 A EP 01945647A EP 01945647 A EP01945647 A EP 01945647A EP 1294673 B1 EP1294673 B1 EP 1294673B1
Authority
EP
European Patent Office
Prior art keywords
aliphatic carboxylic
catalyst
carboxylic acid
acid
lower aliphatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01945647A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1294673A2 (en
Inventor
Etsuko c/o Oita Plant Showa Denko K K KADOWAKI
Tomoyoshi c/o Oita Plant Showa Denko KK HIGASHI
Wataru C/O Oita Plant Showa Denko K K OGUCHI
Hiroshi c/o Oita Plant Showa Denko KK UCHIDA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of EP1294673A2 publication Critical patent/EP1294673A2/en
Application granted granted Critical
Publication of EP1294673B1 publication Critical patent/EP1294673B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density

Definitions

  • the present invention relates to a catalyst for use in producing a lower aliphatic carboxylic acid ester from a lower olefin and a lower aliphatic carboxylic acid, a process for producing the catalyst, and a process for producing a lower aliphatic carboxylic acid ester using the catalyst.
  • the present invention relates to a catalyst for use in producing a lower aliphatic carboxylic acid ester, which contains a specific heteropolyacid salt and which is used in the process for producing a lower aliphatic carboxylic acid ester by esterifying a lower aliphatic carboxylic acid with a lower olefin, wherein the catalyst is contacted with a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols before the reaction; a process for producing the catalyst; and a process for producing a lower aliphatic carboxylic acid ester using the catalyst.
  • a corresponding ester can be produced from a lower aliphatic carboxylic acid and an olefin.
  • a catalyst comprising a heteropolyacid and/or a salt thereof is known to effectively act in this reaction.
  • Specific examples of such a catalyst include those described in Japanese Unexamined Patent Publications No. 4-139148 (JP-A-4-139148), No. 4-13949 (JP-A-4-139149), No. 5-65248 (JP-A-5-65248) and No. 5-294894 (JP-A-5-294894).
  • the catalysts containing at least one salt selected from the group consisting of cesium salts, rubidium salts, thallium salts, ammonium salts and potassium salts of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid disclosed in JP-A-4-139148, JP-A-4-139149 and JP-A-5-65248 exhibit high initial activity and relatively high space time yield.
  • the activity decreases and the space time yield also lowers with the progress of reaction and this was a problem to be solved.
  • JP-A-5-170698 proposes a method of contacting a catalyst described above with water and an organic carboxylic acid or an organic carboxylic acid ester in a gas phase before performing the reaction.
  • a production process of a lower aliphatic carboxylic acid ester using a catalyst subjected to a pre-contacting treatment according to the above-described method it is revealed that the catalyst exhibits high initial activity and the activity scarcely decreases as compared with conventional production processes using a catalyst which is not subjected to the contacting treatment.
  • JP-A-5-294894 discloses a catalyst obtained by loading at least one heteropolyacid salt selected from the group consisting of lithium salts, copper salts, magnesium salts and gallium salts of heteropolyacids on a support and it is revealed that although the method disclosed in JP-A-5-170698 of contacting a catalyst with water and an organic carboxylic acid or an organic carboxylic acid ester in a gas phase before performing the reaction is not used, the catalyst can exhibit initial activity equal thereto or higher than that and can maintain the activity.
  • a circulation process is generally employed mainly for recycling unreacted raw materials so as to increase the reaction efficiency in view of profitability.
  • the catalyst may be damaged and the catalyst life greatly shortened.
  • JP-A-11-269126 discloses a method of removing acetaldehyde impurities at the reactor inlet by distillation or by reacting them with a compound highly reactive with an aldehyde group.
  • JP-A-11-335323 discloses a method of newly providing a step for removing acetaldehyde using an acetaldehyde-removing column and thereby separating it. In either case, however, a new separation step must be provided, therefore, the process becomes very cumbersome and the costs increase.
  • the object of the present invention is to provide a catalyst for use in producing a lower aliphatic carboxylic acid ester, which is used in producing a lower aliphatic carboxylic acid ester from a lower olefin and a lower aliphatic carboxylic acid and which is a catalyst having high initial activity and high space time yield, favored with a catalyst life long enough to endure practical use in industry and capable of reducing the production of by-products; a process for producing the catalyst; and a process for producing a lower aliphatic carboxylic acid ester using the catalyst.
  • the present inventors have made extensive investigations into a catalyst not only capable of exhibiting high initial activity and sufficiently long catalyst life at the reaction of a lower olefin and a lower aliphatic carboxylic acid in a gas phase to produce a lower fatty acid ester, but also reduced in the production of by-products represented by butene and aldehydes which work out to a catalyst poison.
  • a specific step is provided in the preparation of a catalyst, the catalyst can be greatly reduced in the production of by-products harmful to the catalyst, such as butene and aldehydes.
  • the present invention has been accomplished based on this finding.
  • the present invention (I) is a catalyst for use in producing a lower aliphatic carboxylic acid ester, which is used in reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase to produce a lower aliphatic carboxylic acid ester, wherein the catalyst is produced by a process comprising the following first and second steps:
  • the present invention (II) is a process for producing a catalyst for use in producing a lower aliphatic carboxylic acid ester, the catalyst being used in reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase to produce a lower aliphatic carboxylic acid ester, which process comprises the following first and second steps:
  • the present invention (III) is a process for producing a lower aliphatic carboxylic acid ester, comprising reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase in the presence of the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I).
  • the present invention (IV) is a process for producing a lower aliphatic carboxylic acid ester comprising reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase, which process comprises the following first to fourth steps:
  • the present invention (I) is a catalyst for use in producing a lower aliphatic carboxylic acid ester, which is used in reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase to produce a lower aliphatic carboxylic acid ester, wherein the catalyst is produced by a process comprising the following first and second steps:
  • the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I) is a catalyst obtained by a production process comprising the above-described first and second steps.
  • the first step is described below.
  • the heteropolyacid used in the first step comprises a center element and a peripheral element to which oxygen is bonded.
  • the center element is usually silicon or phosphorus but may comprise an optional element selected from various kinds of elements belonging to Groups I to XVII of the Periodic Table.
  • center element examples include cupric ion; divalent beryllium, zinc, cobalt and nickel ions; trivalent boron, aluminum, gallium, iron, cerium, arsenic, antimony, phosphorus, bismuth, chromium and rhodium ions; tetravalent silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese, nickel, platinum, thorium, hafnium and cerium ions and other rare earth ions; pentavalent phosphorus, arsenic, vanadium and antimony ions; hexavalent tellurium ion; and heptavalent iodide ion, however, the present invention is by no means limited thereto.
  • peripheral element include tungsten, molybdenum, vanadium, niobium and tantalum, however, the present invention is by no means limited thereto.
  • heteropolyacids are also known as a "polyoxoanion", a “polyoxometallic salt” or a “metal oxide cluster”.
  • Some well known structures of anions are named after a researcher himself in this field, for example, as Keggin, Wells-Dawson or Anderson-Evans-Perloff structures. There are detailed description in “Porisan no Kagaku, Kikan Kagaku Sousetau (Chemistry of Polyacids, Seasonal Publication for Introduction to Chemistry)” , No. 20, 1993, edited by Japan Chemical Society.
  • Heteropolyacids usually have a high molecular weighty for example, a molecular weight of 700 to 8,500, and include dimeric complexes.
  • heteropolyacid which can be used as the starting material of heteropolyacid salt in the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I) include : Tungstosilicic acid H 4 [SiW 12 O 40 ] ⁇ xH 2 O Tungstophosphoric acid H 3 [PW 12 O 40 ] ⁇ xH 2 O Molybdophosphoric acid H 3 [PMo 12 O 40 ] ⁇ xH 2 O Molybdosilicic acid H 4 [SiMo 12 O 40 ] ⁇ xH 2 O Vanadotungstosilicic acid H 4+n [SiV n W 12-n O 40 ] ⁇ xH 2 O.
  • tungstosilicic acid preferred are tungstosilicic acid, tungstophosphoric acid, molybdophosphoric acid, molybdosilicic acid, vanadotungstosilicic acid and vanadotungstophosphoric acid, and more preferred are tungstosilicic acid, tungstophosphoric acid, vanadotungstosilicic acid and vanadotungstophosphoric acid.
  • the method of the production of the heteropolyacids are not particularly limited and any methods can be used.
  • they may be produced by heating an acidic aqueous solution (a pH of about 1-2) containing a salt of molybdec acid or tungstic acid and a simple oxygen acid of a hetero-atom or a salt thereof.
  • a heteropolyacid compound may be isolated from the resulting aqueous heteropolyacid solution by a method of separation through precipitation as a metal salt, for example.
  • the heteropolyacid salt as used in the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I) is not particularly limited as long as it is a metal salt or an onium salt in which a part or all of hydrogen atoms of the above-described heteropolyacids are substituted.
  • Specific examples thereof include salts of metals such as lithium, sodium, magnesium, barium, copper, gold and gallium, and onium salts, however, the present invention is not limited thereto.
  • preferred are lithium salts, sodium salts, gallium salts, copper salts and gold salts, more preferred are lithium salts, sodium salts and copper salts.
  • Heteropolyacids have a relatively high solubility in a polar solvent such as water and other oxygen-containing solvents particularly when the heteropolyacids are free acids or comprise several salts, and the solubility can be controlled by appropriately selecting the counter ion.
  • Examples of the starting material for the metal element or onium moiety of forming the heteropolyacid salt in the present invention include lithium nitrate, lithium acetate, lithium sulfate, lithium sulfite, lithium carbonate, lithium phosphate, lithium oxalate, lithium nitrite, lithium chloride, lithium citrate, sodium nitrate, sodium acetate, sodium sulfate, sodium carbonate, monosodium phosphate, disodium phosphate, sodium oxalate, sodium nitrite, sodium chloride, sodium citrate, magnesium nitrate hexahydrate, magnesium acetate tetrahydrate, magnesium sulfate, magnesium carbonate, magnesium phosphate tricosahydrate, magnesium oxalate dihydrate, magnesium chloride, magnesium citrate, barium nitrate, barium acetate, barium sulfate, barium carbonate, barium hydrogenphosphate, barium oxalate monohydrate, barium sulfite, barium
  • heteropolyacid salt which can be used in the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I) include lithium salt of tungstosilicic acid, sodium salt of tungstosilicic acid, copper salt of tungstosilicic acid, gold salt of tungstosilicic acid, gallium salt of tungstosilicic acid, lithium salt of tungstophosphoric acid, sodium salt of tungstophosphoric acid, copper salt of tungstophosphoric acid, gold salt of tungstophosphoric acid, gallium salt of tungstophosphoric acid, lithium salt of molybdophosphoric acid, sodium salt of molybdophosphoric acid, copper salt of molybdophosphoric acid, gold salt of molybdophosphoric acid, gallium salt of molybdophosphoric acid, lithium salt of molybdosilicic acid, sodium salt of molybdosilicic acid, copper salt of molybdosilicic acid, gold salt of molybdosilicic acid, gallium salt of mo
  • lithium salt of tungstosilicic acid sodium salt of tungstosilicic acid, copper salt of tungstosilicic acid, gold salt of tungstosilicic acid, gallium salt of tungstosilicic acid, lithium salt of tungstophosphoric acid, sodium salt of tungstophosphoric acid, copper salt of tungstophosphoric acid, gold salt of tungstophosphoric acid, gallium salt of tungstophosphoric acid, lithium salt of molybdophosphoric acid, sodium salt of molybdophosphoric acid, copper salt of molybdophosphoric acid, gold salt of molybdophosphoric acid, gallium salt of molybdophosphoric acid, lithium salt of molybdosilicic acid, sodium salt of molybdosilicic acid, copper salt of molybdosilicic acid, gold salt of molybdosilicic acid, gallium salt of molybdosilicic acid, lithium salt of vanadotungstosilicic acid, sodium salt of vanadotungstosilicic acid, copper salt of vanadotungstosilicic
  • lithium salt of tungstosilicic acid sodium salt of tungstosilicic acid, copper salt of tungstosilicic acid, gold salt of tungstosilicic acid, gallium salt of tungstosilicic acid, lithium salt of tungstophosphoric acid, sodium salt of tungstophosphoric acid, copper salt of tungstophosphoric acid, gold salt of tungstophosphoric acid, gallium salt of tungstophosphoric acid, lithium salt of vanadotungstosilicic acid, sodium salt of vanadotungstosilicic acid, copper salt of vanadotungstosilicic acid, gold salt of vanadotungstosilicic acid, gallium salt of vanadotungstosilicic acid, lithium salt of vanadotungstophosphoric acid, sodium salt of vanadotungstophosphoric acid, copper salt of vanadotungstophosphoric acid, gold salt of vanadotungstophosphoric acid and gallium salt of vanadotungstophosphoric acid.
  • the heteropolyacid salt as a catalytic activity component is supported on a support.
  • Substances which can be used as the support are not particularly limited and porous substances commonly used as a support may be used. Specific examples thereof include those comprising silica, diatomaceous earth, montmorillonite, titania, activated carbon, alumina and silica alumina, preferably silica, silica alumina and montmorillonite.
  • the support is also not limited on the shape thereof and may be in the powder, spherical, pellet-like or any other form. A sphere or pellet-like form is preferred.
  • the particle size is not particularly limited and although the preferred particle size varies depending on the reaction form, the average diameter is preferably from 2 to 10 mm in the case of use in a fixed bed system and from powder to 5 mm in the case of use in a fluidized bed system.
  • the support is most preferably a spherical or pellet-form siliceous support.
  • the method for loading the heteropolyacid salt on the support in the first step of the catalyst for producing a lower aliphatic carboxylic acid ester of the present invention (I) is roughly classified into the following three groups (1) to (3).
  • the heteropolyacid and the starting material for the element or moiety of forming the salt each can be loaded by dissolving or suspending it in an appropriate solvent.
  • the solvent may be any as long as it can uniformly dissolve or suspend the desired heteropolyacid, a salt thereof and the starting material for the element or moiety of forming the salt, and examples of the solvent which can be used include water, an organic solvent and a mixture thereof. Among these, preferred are water, alcohols and carboxylic acids.
  • the method used for the dissolution or suspension may also be any as long as it can uniformly dissolve or suspend the desired heteropolyacid, a salt thereof and the starting material for the element or moiety of forming the salt.
  • a free acid a free acid which can dissolve may be dissolved as it is in a solvent and even in the case of a free acid which cannot completely dissolve, if the free acid can be uniformly suspended by forming it into fine powder, the free acid may be suspended as such.
  • a solution or suspension obtained by dissolving or suspending a heteropolyacid in a solvent is absorbed to a support to thereby load the heteropolyacid on the support and, then, a solution or suspension of a starting material for the element, or moiety of forming a desired salt is absorbed to the support to thereby load the element or moiety.
  • a neutralization reaction proceeds on the support, as a result, a heteropolyacid salt supported catalyst can be prepared.
  • a heteropolyacid and a starting material for the element or moiety of forming the salt are dissolved or suspended together or separately and then mixed to prepare a uniform solution or suspension, and the solution or suspension is absorbed to a support, thereby loading the heteropolyacid and the element or moiety.
  • a uniform solution or suspension may be obtained in the same manner as in the case of a free acid.
  • a solution or suspension of a starting material for the element or moiety of forming the salt is previously prepared, the solution or suspension is absorbed to a support to thereby load the element or moiety, and then a desired heteropolyacid is loaded.
  • This method includes a method of using an element or moiety which is previously contained in the support and which can form a heteropolyacid salt.
  • a part or all of the elements previously contained in a support sometimes act to form a salt of a heteropolyacid when the heteropolyacid is loaded, and as a result, a heteropolyacid salt is formed.
  • examples of such an element include potassium, sodium, calcium, iron, magnesium, titanium and aluminum, however, the present invention is not limited thereto.
  • the kind of the element previously contained in a support and the amount thereof can be determined by a chemical analysis such as inductively coupled plasma emission spectrometry (hereinafter referred to as "ICP"), fluorescent X-ray method and atomic absorption method.
  • ICP inductively coupled plasma emission spectrometry
  • the kind and the amount of the element vary depending on the support, however, potassium, sodium, calcium, iron, magnesium, titanium and aluminum are sometimes contained in a relatively large amount and the content thereof is approximately from 0.001 to 5.0% by mass. Therefore, depending on the combination of a support and a heteropolyacid, the element previously contained in the support may be in an amount large enough to form a salt, though this may vary depending on the kind and the amount of the heteropolyacid to be supported.
  • the method for loading a solution or suspension of heteropolyacid or a salt thereof on a support is not particularly limited and a known method may be used.
  • the catalyst may be prepared by dissolving a heteropolyacid in a distilled water corresponding to the liquid absorption amount of the support used and impregnating the solution into a support.
  • the catalyst may be prepared using an excess aqueous heteropolyacid solution by impregnating it into a support while appropriately moving the support in the heteropolyacid solution and then removing the excess acid by filtration.
  • the volume of the solution or suspension used at this time varies depending on the support used or the loading method thereon.
  • the thus-obtained wet catalyst is suitably dried by placing it in a heating oven for a few hours.
  • the drying method is not particularly limited and any method such as of a standing or belt conveyor system may be used. After drying, the catalyst is cooled to the ambient temperature in a desiccator so as not to absorb moisture.
  • the amount of the heteropolyacid salt supported in the heteropolyacid salt supported catalyst can be simply calculated by subtracting the weight of the support used from the weight after drying of the catalyst prepared.
  • the amount supported may be more exactly determined by a chemical analysis such as ICP, fluorescent X-ray method or atomic absorption method.
  • the amount of the heteropolyacid salt supported is preferably from 10 to 150% by mass, more preferably from 30 to 100% by mass, based on the entire weight of the support.
  • the heteropolyacid salt content is less than 10% by mass, the content of active components in the catalyst is too small and the activity per the catalyst unit weight may disadvantageously decrease. If the heteropolyacid salt content exceeds 150% by mass, the effective pore volume may decrease, as a result, the effect owing to the increase in the supported amount may not be brought out and at the same time, coking may be disadvantageously liable to occur to greatly shorten the catalyst life.
  • the second step is described below.
  • the second step in the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I) is a step for contacting the heteropolyacid salt supported catalyst obtained in the first step with a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin.
  • contacting refers to bringing the heteropolyacid salt supported catalyst obtained in the first step into contact with a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin.
  • the method for the contacting is not particularly limited and for example, the following methods may be used.
  • a method of filling the supported catalyst obtained in the first step into a vessel and contacting the gas therewith for example, a method of filling the supported catalyst obtained in the first step into a vessel and contacting the gas therewith, or a method of filling the supported catalyst obtained in the first step into, in place of the vessel, a reactor where the production process of a lower aliphatic carboxylic acid ester is performed later, and contacting the gas therewith before feeding reaction starting materials, may be used.
  • any shape such as vertical type or horizontal type may be used without any particular limit.
  • the preferred embodiment of the second step includes a method of filling the supported catalyst obtained in the first step into a reactor which is used in reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase to produce a lower aliphatic carboxylic acid ester, and then contacting therewith a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin before feeding the reaction starting materials.
  • the reaction may be performed in either a closed circulatory system or a flow system.
  • the second step is preferably performed under conditions not less than the dew point of the gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin. If the conditions are less than the dew point of the gas, a part of the gas may turn into a liquid. In this case, the heteropolyacid salt supported on the catalyst in the first step or other catalyst components supported, as desired, may dissolve out to change the catalyst composition, and in the worst case, the catalyst may be deactivated. As long as the catalyst is not adversely affected, the conditions in performing the second step are not particularly limited.
  • the preferred embodiment of the conditions at the dew point or more of the gas may vary depending on the composition of the gas or the pressure or the like in the practice of the step, however, the contact temperature is preferably from 80 to 300°C, more preferably from 100 to 260°C.
  • the contact pressure is not particularly limited and may be either normal pressure or raised pressure.
  • the contact pressure is preferably from 0 to 3 MPaG (gauge pressure), more preferably from 0 to 2 MPaG (gauge pressure).
  • the lower aliphatic carboxylic acid in a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin used in the second step is a lower aliphatic carboxylic acid having from 1 to 6 carbon atoms. Specific examples thereof include formic acid, acetic acid, propionic acid, n-butyric acid and isobutyric acid. Among these, preferred are acetic acid and propionic acid.
  • the lower aliphatic alcohol in a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin used in the second step is a lower aliphatic alcohol having from 1 to 6 carbon atoms.
  • Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. Among these, preferred are methanol, ethanol and n-propanol.
  • composition of the gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin used in the second step is not particularly limited, and water, a lower aliphatic carboxylic acid and a lower aliphatic alcohol can be mixed at any ratio.
  • composition of the gas may be constant from the beginning to the end of contacting or may vary according to the contacting time or the stage of contacting.
  • the gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin used in the second step is more preferably water alone or a mixed gas of water and acetic acid, still more preferably a mixed gas of water and acetic acid because the effect can be provided within a short time.
  • the gas hourly space velocity (hereinafter referred to as "GHSV"), which is the speed of feeding the gas in performing the contact with a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols used in the second step, is not particularly limited.
  • the GHSV is preferably from 100 to 7,000 hr -1 , more preferably from 300 to 3,000 hr -1 .
  • the contacting may also be performed by feeding a constant amount of the gas and enclosing it in a vessel.
  • the contacting time is not particularly limited, however, it is preferably from 0.5 to 200 hours, more preferably from 0.5 to 100 hours, and most preferably from 0.5 to 50 hours.
  • the optimal time varies depending on the composition and concentration of the gas, the temperature and pressure at the contacting, and the catalyst component.
  • the effect of the second step may not be fully brought out, whereas if the contacting time is prolonged, the effect may be liable to increase but even if the contacting time is prolonged to exceed 200 hours, the effect may not increase any more, moreover, in the case where gas is contacted in the flowing state, the amount of the gas used may increase and this is not preferred in view of the profitability.
  • the present invention (II) is described below.
  • the present invention (II) is a process for producing a catalyst for use in producing a lower aliphatic carboxylic acid ester, the catalyst being used in reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase to produce a lower aliphatic carboxylic acid ester, which process comprises the following first and second steps:
  • the heteropolyacid salt and the support used in the first step, the method for loading the heteropolyacid salt on a support performed in the first step, the method for measuring the amount of the heteropolyacid salt supported, and the preferred amount of the heteropolyacid salt supported on a support may be the same as in the present invention (I).
  • the method for contacting the catalyst with a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin performed in the second step, the conditions therefor such as temperature, pressure, GHSV and time, the lower aliphatic carboxylic acid and lower aliphatic alcohol used for the gas, and the compositional ratio of the gas to which water is further added, may be the same as in the present invention (I).
  • Examples of the step which is provided, as desired, include a step for loading a third component so as to more improve the catalytic activity.
  • this loading operation may be performed simultaneously with the operation of loading the heteropolyacid salt in the first step, if possible.
  • the catalyst may further be contacted with another gas.
  • the present invention (III) is described below.
  • the present invention (III) is a process for producing a lower aliphatic carboxylic acid ester, comprising reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase in the presence of the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I).
  • a gas phase reaction is not particularly limited on the reaction form and the reaction may be performed in any form such as in a fixed bed system or fluidized bed system.
  • the shape of the support which governs the shape or size of the catalyst may be selected in the range from powder to a compact formed into a size of several mm according to the reaction form employed.
  • the lower olefin which is used in the process for producing a lower aliphatic carboxylic acid ester of the present invention (III) are ethylene, propylene, n-butene, isobutene and a mixture of two or more thereof.
  • the lower aliphatic carboxylic acid is a carboxylic acid having from 1 to 4 carbon atoms and specific examples thereof include formic acid, acetic acid, propionic acid, butyric acid, acrylic acid and methacrylic acid.
  • the ratio between the lower olefin and the lower aliphatic carboxylic acid used as the starting materials is not particularly limited.
  • the lower olefin is preferably used in an equimolar or excess amount based on the lower aliphatic carboxylic acid.
  • a small amount of water is preferably added to the starting materials.
  • the amount of a by-product such as an alcohol or an ether may disadvantageously increase.
  • the amount of water added is preferably from 0.5 to 15 mol%, more preferably from 2 to 8 mol%, in terms of the molar ratio of water to the total amount of the lower olefin, the lower aliphatic carboxylic acid, as the starting materials, and water added.
  • reaction conditions such as temperature and pressure preferred in the process for producing a lower aliphatic carboxylic acid ester of the present invention (III), may vary depending on the lower olefin and the lower aliphatic carboxylic acid used as the starting materials.
  • the reaction conditions such as temperature and pressure are preferably combined so that the starting materials each can be kept in the gas state and the reaction can satisfactorily proceed.
  • the temperature is preferably from 120 to 300°C, more preferably from 140 to 250°C.
  • the pressure is preferably from 0 to 3 MPaG (gauge pressure), more preferably from 0 to 2 MPaG (gauge pressure).
  • the starting materials each is not particularly limited on the GHSV. If the GHSV is excessively high, the gas may pass through before the reaction satisfactorily proceeds, whereas if it is too low, problems, such as reduction in the productivity, may arise.
  • the GHSV is preferably from 100 hr -1 to 7,000 hr -1 , more preferably from 300 hr -1 to 3,000 hr -3 .
  • the unreacted lower olefin and also alcohol and ether produced as by-products in the reaction may be recycled and used as they are.
  • the substances which are harmful to the catalyst for use in producing a lower aliphatic carboxylic acid ester, such as butene and an aldehyde are difficult to separate from olefin, alcohol, ether and the like, and may sometimes be transferred to a reactor. In such a case, the catalyst may be conspicuously reduced in activity or extremely shortened in the life.
  • the process for producing a lower aliphatic carboxylic acid ester of the present invention (III) using the catalyst for use in producing a lower aliphatic carboxylic acid ester of the present invention (I) can greatly decrease the production of those by-products at the stage of reaction, therefore, the present invention (III) is particularly effective in the case where the above-described recycling system is employed in the production process.
  • the present invention (IV) is described below.
  • the present invention (IV) is a process for producing a lower aliphatic carboxylic acid ester, comprising reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase, which process comprises the following first to fourth steps:
  • the first step is described below.
  • the first step in the process for producing a lower aliphatic carboxylic acid ester of the present invention (IV) is a step of loading a heteropolyacid salt on a support to obtain a heteropolyacid salt supported catalyst.
  • the heteropolyacid salt and the support used in the first step, the method for loading the heteropolyacid salt on a support performed in the first step, the method for measuring the amount of the heteropolyacid salt supported, and the preferred amount of the heteropolyacid salt supported on a support may be the same as in the present invention (I).
  • the second step is described below.
  • the second step in the process for producing a lower aliphatic carboxylic acid ester of the present invention (IV) is a step of filling the heteropolyacid salt supported catalyst obtained in the first step, into a reactor for use in reacting a lower olefin with a lower aliphatic carboxylic acid in a gas phase.
  • the second step is a step of filling the heteropolyacid salt supported catalyst into a reactor for use in the reaction of a lower olefin with a lower aliphatic carboxylic acid, so that the second step of the present invention (I) which is the catalyst for use in producing a lower aliphatic carboxylic acid ester, or the second step of the present invention (II) which is the process for producing a catalyst for use in producing a lower aliphatic carboxylic acid ester, namely, a step of contacting the heteropolyacid salt supported catalyst obtained in the first step with a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin, can be performed in the reactor without using another vessel.
  • the reactor used in the second step is not particularly limited.
  • a fixed bed gas phase-type reactor is preferred, and a reactor having a form of multi-tube system and/or multi-layer system is more preferred.
  • a reactor having a form of multi-tube system and/or multi-layer system is superior in the reaction results, thermal efficiency, eases of control and the like.
  • the present invention is not limited thereto.
  • the term "filling the catalyst into a reactor” refers to placing the catalyst in a predetermined site of the reactor.
  • the site and the method for the placement and in the case where the reactor uses a fixed bed system, the method for fixing the catalyst may vary depending on the form of the reactor and these are not particularly limited.
  • Specific examples of the reactor include Fig. C ⁇ 4 ⁇ 43 "Methanol Treating Gas Phase Reactor” in the item of "4) Fixed catalyst gas phase reactor", described in Kagaku Sochi Binran (Chemical Apparatuses Handbook) , 2nd ed., 3rd imp., pp. 905 to 906, edited by Society of Japan Chemical Engineering, published by Maruzen (February 20, 1980).
  • the third step is described below.
  • the third step in the process for producing a lower aliphatic carboxylic acid ester of the present invention (IV) is a step of contacting a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin with the heteropolyacid salt supported catalyst filled in the reactor.
  • the method for contacting the catalyst with a gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin performed in the third step, the conditions such as temperature, pressure, space velocity and time, the lower aliphatic carboxylic acid and lower aliphatic alcohol used for the gas, and the compositional ratio of the gas to which water is further added, may be the same as the second step of the present invention (I).
  • the conditions therefor are not particularly limited, and the preferred conditions are considered to vary depending on the form, shape, size or constructive material of the reactor used for the contacting.
  • the contacting may be performed under the conditions described above for the second step of the present invention (I).
  • the fourth step is described below.
  • the fourth step of the present invention (IV) is a step of passing a mixed gas containing the lower olefin and the lower aliphatic carboxylic acid through the heteropolyacid salt supported catalyst after the third step, to obtain the lower aliphatic carboxylic acid ester.
  • the lower olefin and lower aliphatic carboxylic acid used in the fourth step, the amount ratio thereof, the conditions such as addition of water, temperature, pressure and GHSV on performing the fourth step, and the recycling operation mainly of the unreacted lower olefin may be the same as in the process for the producing a lower aliphatic carboxylic acid ester of the present invention (III).
  • the third step and the fourth step of the present invention (IV) are clearly distinguished. After judging that the contacting in the third step is finished, the flow of the gas containing at least one member selected from the group consisting of water, lower aliphatic carboxylic acids and lower aliphatic alcohols without any olefin is once stopped or the temperature is further lowered to complete the third step and, thereafter, the starting material gas containing a lower olefin and a lower aliphatic carboxylic acid is passed as the reaction gas in the fourth step.
  • the contacting in the third step is preferably performed using a lower aliphatic carboxylic acid corresponding to the ester as an objective product of the process for producing a lower aliphatic carboxylic acid ester of the present invention (IV).
  • a lower aliphatic carboxylic acid corresponding to the ester as an objective product of the process for producing a lower aliphatic carboxylic acid ester of the present invention (IV).
  • one of the preferred practical embodiments is a method of performing the contacting in the third step using a mixed gas of water and acetic acid for a constant time under constant conditions, then varying various conditions within the reactor, such as temperature, pressure and GHSV, to fit the production process of a lower aliphatic carboxylic acid ester, and adding ethylene to the gas introduced into the reactor.
  • the present invention (IV) is not limited thereto.
  • the analysis was performed under the following conditions using an absolute calibration curve process by sampling 50 ml of the effluent gas and passing the entire amount thereof into a 1 ml gas sampler attached to the gas chromatograph.
  • the analysis was performed using an internal standard method by injecting 0.4 ⁇ l of an analysis solution obtained by adding 1 ml of 1,4-dioxane as an internal standard to 10 ml of the reaction solution.
  • Support 1 was preliminarily dried for 4 hours in a (hot-air type) drier previously adjusted to 110°C. After the preliminary drying, 1 liter of the support was measured on the bulk density using a 1 liter measuring cylinder. Tungstosilicic acid was weighed to the amount shown in Table 2 and after adding thereto 15 ml of pure water, uniformly dissolved. To this impregnating solution, pure water was further added to make the liquid amount shown in Volume of Solution Prepared of Table 2. Thereafter, the preliminarily dried support was weighed to the amount shown in Table 2, added to the impregnating solution and impregnated with the solution while thoroughly stirring.
  • the support impregnated with the solution was transferred to a porcelain dish, air-dried for 1 hour and then dried in a hot-air type drier adjusted to 150 °C for 5 hours. After the drying, the catalyst was transferred in a desiccator and left standing to cool to room temperature. This is designated as a "tungstosilicic acid supported catalyst".
  • lithium nitrite was weighed to the amount shown in Table 2 and after adding thereto 15 ml of pure water, uniformly dissolved.
  • pure water was added to make the liquid amount shown in Volume of Solution Prepared shown of Table 2 and then the solution was uniformly stirred.
  • the tungstosilicic acid supported catalyst after cooling was added, in the entire amount, to the impregnating solution and impregnated with the solution while thoroughly stirring.
  • the support impregnated with the solution was transferred to a porcelain dish, air-dried for 1 hour and then dried in a hot-air type drier adjusted to 150°C for 5 hours. After the drying, the catalyst was transferred in a desiccator and left standing to cool to room temperature. The weight of the thus-obtained catalyst was measured.
  • Support 1 was preliminarily dried for 4 hours in a (hot-air type) drier previously adjusted to 110°C. After the preliminary drying, 1 liter of the support was measured on the bulk density using a 1 liter measuring cylinder. Tungstosilicic acid and sodium acetate each was weighed to the amount shown in Table 2 and after adding thereto 15 ml of pure water, uniformly dissolved to obtain an aqueous solution of Na 0.1 H 3.9 SiW 12 O 40 (impregnating solution). To this impregnating solution, pure water was further added to make the liquid amount shown in Volume of Solution Prepared of Table 2.
  • the preliminarily dried support was weighed to the amount shown in Table 2, added to the impregnating solution and impregnated with the solution while thoroughly stirring.
  • the support impregnated with the solution was transferred to a porcelain dish, air-dried for 1 hour and then dried in a hot-air type drier adjusted to 150°C for 5 hours. After the drying, the catalyst was transferred in a desiccator and left standing to cool to room temperature. The weight of the thus-obtained catalyst was measured.
  • catalysts were prepared by changing the kind and weight of the support, the kind and weight of the catalyst component, and the weight of the neutralization salt as shown in Table 2 in Preparation Process of Catalyst 1.
  • the loading on a support was performed in the same manner as in Preparation Process of Catalyst 1.
  • These catalysts were prepared by changing the kind and weight of the support, the kind and weight of the catalyst component, and the weight of the neutralization salt as shown in Table 2 in Preparation Process of Catalyst 2.
  • the loading on a support was performed in the same manner as in Preparation Process of Catalyst 2.
  • Support 4 was preliminarily dried for 4 hours in a (hot-air type) drier previously adjusted to 110°C. After the preliminary drying, 1 liter of the support was measured on the bulk density using a 1 liter measuring cylinder. Lithium nitrate was weighed to the amount shown in Table 2 and after adding thereto 15 ml of pure water, uniformly dissolved. To this impregnating solution, pure water was further added to make the liquid amount shown in Volume of Solution Prepared of Table 2. Thereafter, the preliminarily dried support was weighed to the amount shown in Table 2, added to the impregnating solution and impregnated with the solution while thoroughly stirring.
  • the support impregnated with the solution was transferred to a porcelain dish, air-dried for 1 hour and then dried in a hot-air type drier adjusted to 150°C for 5 hours. After the drying, the catalyst was transferred in a desiccator and left standing to cool to room temperature. This is designated as a "lithium nitrate supported catalyst”. Tungstosilicic acid was weighed to the amount shown in Table 2 and after adding thereto 15 ml of pure water, uniformly dissolved.
  • This catalyst was prepared by changing the kind and weight of the support, the kind and weight of the catalyst component, and the weight of the neutralization salt as shown in Table 2 in Preparation Process of Catalyst 8.
  • the loading on a support was performed in the same manner as in Preparation Process of Catalyst 8.
  • contacted catalyst the catalyst used for the contacting
  • the outlet gas remaining uncondensed (hereinafter referred to as an "uncondensed gas”) was measured on the gas flow rate for the same predetermined time as in the condensed solution and then 50 ml of the gas was sampled and analyzed. The results are shown in Table 3.
  • Example 4 In the same manner as in Example 4, 40 ml of the catalyst shown in Table 3 was filled into a reaction tube and contacted under the contacting conditions shown in Table 3. Thereafter, a reaction was performed in the same manner as in Example 5. The reaction results are shown in Table 3.
  • This catalyst can maintain its catalytic activity without performing the removal of by-products, therefore, the catalyst is very useful particularly in practicing the process for producing a lower aliphatic carboxylic acid ester by employing a recycling system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
EP01945647A 2000-06-27 2001-06-27 Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst Expired - Lifetime EP1294673B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2000192964 2000-06-27
JP2000192964 2000-06-27
US21880300P 2000-07-18 2000-07-18
US218803P 2000-07-18
PCT/JP2001/005532 WO2002000589A2 (en) 2000-06-27 2001-06-27 Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst

Publications (2)

Publication Number Publication Date
EP1294673A2 EP1294673A2 (en) 2003-03-26
EP1294673B1 true EP1294673B1 (en) 2005-03-16

Family

ID=26594780

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01945647A Expired - Lifetime EP1294673B1 (en) 2000-06-27 2001-06-27 Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst

Country Status (7)

Country Link
EP (1) EP1294673B1 (zh)
CN (1) CN1195726C (zh)
AT (1) ATE291005T1 (zh)
AU (1) AU6784701A (zh)
BR (1) BR0111964A (zh)
DE (1) DE60109449D1 (zh)
WO (1) WO2002000589A2 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002020157A2 (en) * 2000-09-07 2002-03-14 Showa Denko K. K. Heteropolyacid catalyst for producing lower aliphatic carboxylic acid ester
CN1452511A (zh) * 2000-09-07 2003-10-29 昭和电工株式会社 生产低级脂族羧酸酯的催化剂
TWI272123B (en) * 2002-12-20 2007-02-01 Showa Denko Kk Heteropolyacid and/or its salt supported catalyst, production process of the catalyst and production process of compound using the catalyst
JP5376804B2 (ja) 2004-09-22 2013-12-25 イネオス ユーロープ リミテッド シリカ支持体、それから製造されるヘテロポリ酸触媒およびシリカ支持ヘテロポリ酸触媒を使用するエステル合成

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5241106A (en) * 1991-10-22 1993-08-31 Mitsui Toatsu Chemicals, Inc. Process for producing ethyl acetate
JP3012059B2 (ja) * 1991-11-05 2000-02-21 昭和電工株式会社 低級脂肪酸エステルの製造方法
EP0562139B1 (en) * 1992-03-25 1995-12-13 Showa Denko Kabushiki Kaisha Process for preparation of lower fatty acid ester
DE69618032T2 (de) * 1995-08-02 2002-06-27 Bp Chem Int Ltd Estersynthese
EG21992A (en) * 1998-01-22 2002-05-31 Bp Chem Int Ltd Ester synthesis
GB9815117D0 (en) * 1998-07-14 1998-09-09 Bp Chem Int Ltd Ester synthesis
DE60036002T2 (de) * 1999-06-03 2008-05-21 Showa Denko K.K. Verfahren für die herstellung von fettsäureestern

Also Published As

Publication number Publication date
CN1195726C (zh) 2005-04-06
EP1294673A2 (en) 2003-03-26
WO2002000589A3 (en) 2002-04-18
CN1446189A (zh) 2003-10-01
AU6784701A (en) 2002-01-08
BR0111964A (pt) 2003-04-01
DE60109449D1 (de) 2005-04-21
ATE291005T1 (de) 2005-04-15
WO2002000589A2 (en) 2002-01-03

Similar Documents

Publication Publication Date Title
US20040152915A1 (en) Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst, and process for producing lower aliphatic carboxylic acid ester using the catalyst
US7553794B2 (en) Heteropolyacid and or its salt supported catalyst, production process of the catalyst and production process of compound using the catalyst
EP1324825A2 (en) Heteropolyacid catalyst for producing lower aliphatic carboxylic acid ester
EP1294673B1 (en) Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst
US20040143132A1 (en) Regeneration of catalyst for use in production of lower aliphatic carboxylic acid ester and production of lower aliphatic carboxylic acid ester
US20030032837A1 (en) Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst
US20040186015A1 (en) Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst, and process for producing lower aliphatic carboxylic acid ester using the catalyst
US20040242918A1 (en) Support and catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst
EP1224158B1 (en) Process for producing esters
EP1320517B1 (en) Process for producing lower aliphatic carboxylic acid ester
US20070173663A1 (en) Production and use of supported catalysts
JP4565919B2 (ja) 低級脂肪族カルボン酸エステル製造用触媒、該触媒の製造方法及び該触媒を用いた低級脂肪族カルボン酸エステルの製造方法
JP2002079090A (ja) 低級脂肪族カルボン酸エステル製造用触媒、該触媒の製造方法、及び該触媒を用いた低級脂肪族カルボン酸エステルの製造方法
JP4329163B2 (ja) 低級脂肪族エステル製造用触媒、該触媒の製造方法、及び該触媒を用いた低級脂肪酸エステルの製造方法
US20030118497A1 (en) Support for use in catalyst for producing lower aliphatic carboxylic acid ester, catalyst for producing lower aliphatic carboxylic acid ester using the support, process for producing the catalyst, and process for producing lower aliphatic carboxylic acid ester using the catalyst
US20040181088A1 (en) Production of lower aliphatic carboxylic acid ester
JP4123670B2 (ja) エステルの製造方法
US6849759B1 (en) Process for producing esters
US20050203310A1 (en) Process for the production of aliphatic carboxylic acid esters
EP1353749A2 (en) Catalyst for producing lower aliphatic carboxylic acid esters
JP4859742B2 (ja) 酢酸製造用担持型触媒の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030109

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17Q First examination report despatched

Effective date: 20030611

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050316

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050316

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050316

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050316

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050316

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050316

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050316

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050316

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60109449

Country of ref document: DE

Date of ref document: 20050421

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050616

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050627

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050627

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050627

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050630

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20050316

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050907

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20051219

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

EN Fr: translation not filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050316

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090624

Year of fee payment: 9

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100627